Process for oligomerization of butene with determination of the proportion of acidic catalysis

Patent metadata

Field	Value
Publication number	US-10633302-B2
Application number	US-201916509532-A
Country	US
Kind code	B2
Filing date	Jul 12, 2019
Priority date	Jul 25, 2018
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

The invention provides a process for oligomerization of n-butenes using a nickel-containing aluminosilicate catalyst to produce a product mixture whose ratio of 4,4-dimethylhexene to 3,4-dimethylhexene is determined and monitored. The invention further relates to a process for determining the ratio of the amount of the formed 4,4-dimethylhexene or of the formed 3-ethyl-2-methylpentene to the amount of the formed 3,4-dimethylhexene.

First claim

The invention claimed is:

1. A process for oligomerization of n-butenes comprising:
contacting a reactant stream comprising n-butenes with a mesoporous, nickel-containing aluminosilicate catalyst to form a product mixture;
monitoring a ratio of the amount of formed 4,4-dimethylhexene to the amount of formed 3,4-dimethylhexene in the product mixture; and
replacing the catalyst with fresh catalyst when the ratio exceeds a threshold value for the ratio, wherein the threshold value for the ratio is 0.05 or less.

2. The process according to claim 1 , wherein the process for oligomerization is performed at a temperature in the range from 50° C. to 200° C.

3. The process according to claim 1 , wherein the process for oligomerization is performed at a pressure in the range from 10 bar to 70 bar.

4. The process according to claim 1 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in the process for oligomerization contains nickel, calculated as nickel oxide NiO, in an amount of 0.1% to 51% by weight based on the total composition of the mesoporous nickel-containing aluminosilicate catalyst.

5. The process according to claim 1 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in the process for oligomerization has an Si/Al ratio of 1 to 100.

6. The process according to claim 1 , wherein the mesoporous nickel-containing aluminosilicate catalyst contains no titanium dioxide and/or no zirconium dioxide.

7. The process according to claim 1 , wherein the process for oligomerization is performed at a temperature in the range from 60° C. to 130° C.

8. The process according to claim 1 , wherein the process for oligomerization is performed at a pressure in the range from 15 bar to 42 bar.

9. The process according to claim 1 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in the process for oligomerization contains nickel, calculated as nickel oxide NiO, in an amount of 1% to 42% by weight based on the total composition of the mesoporous nickel-containing aluminosilicate catalyst.

10. The process according to claim 1 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in the process for oligomerization has an Si/Al ratio of 2 to 80.

11. A process for determining a ratio of an amount of formed 4,4-dimethylhexene or of formed 3-ethyl-2-methylpentene to an amount of formed 3,4-dimethylhexene, the process comprising the steps of:
a) oligomerizing a reactant stream comprising n-butenes with a mesoporous nickel-containing aluminosilicate catalyst to form a product stream comprising C8 isomers;
b) quantitative analysis of the product stream obtained from the oligomerization to determine the amounts of the C8 isomers including n-octene, 3-methylheptene, 3,4-dimethylhexene, 4,4-dimethylhexene, 2,3-dimethylhexene and 3-ethyl-2-methylpentene formed during oligomerization;
c) determining the ratio of the amount of the formed 4,4-dimethylhexene or of the formed 3-ethyl-2-methylpentene to the amount of the formed 3,4-dimethylhexene; and
d) replacing the catalyst in step a) with fresh catalyst when the ratio exceeds a threshold value for the ratio, wherein the threshold value for the ratio is 0.05 or less.

12. The process according to claim 11 , wherein the oligomerization in step a) is performed at a temperature in the range from 50° C. to 200° C.

13. The process according to claim 11 , wherein the oligomerization in step a) is performed at a pressure in the range from 10 bar to 70 bar.

14. The process according to claim 11 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in step a) contains nickel, calculated as nickel oxide NiO, in an amount of 0.1% to 51% by weight based on the total composition of the mesoporous nickel-containing aluminosilicate catalyst.

15. The process according to claim 11 , wherein the mesoporous nickel-containing aluminosilicate catalyst employed in the oligomerization in step a) has an Si/Al ratio of 1 to 100.

16. The process according to claim 11 , wherein the mesoporous nickel-containing aluminosilicate catalyst in step a) contains no titanium dioxide and/or no zirconium dioxide.

17. The process according to claim 11 , wherein the oligomerization is performed at a weight hourly space velocity (WHSV) of between 1 h-1 and 190 h-1.

18. The process according to claim 11 , wherein the quantitative analysis in step b) is performed by gas chromatography.

19. The process according to claim 11 , wherein the oligomerization in step a) is performed at a temperature in the range from 60° C. to 130° C.

20. The process according to claim 11 , wherein the oligomerization in step a) is performed at a pressure in the range from 15 bar to 42 bar.

Assignees

• Evonik Degussa Gmbh
• Evonik Operations Gmbh

Inventors

• Nadolny Fabian
• Peitz Stephan
• Stochniol Guido
• Franke Robert
• Alscher Felix
• Breitkopf Cornelia
• Reschetilowski Wladimir

Classifications

• G01N2030/8854

  involving hydrocarbons · CPC title

• C07C2/12 Primary

  with crystalline alumino-silicates {or with catalysts comprising} molecular sieves · CPC title

• B01J37/0201

  Impregnation · CPC title

• G01N30/88

  Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 · CPC title

• B01J23/755

  Nickel · CPC title